This application claims priority to Japanese Patent Application No.P2000-242750.
1. Field of the Invention
The present invention relates to polishing of a metal film, and in particular, to a method of polishing in an interconnect-fabrication process for producing semiconductor devices.
2. Description of the Background
In recent years, with rapid progress and development in the techniques available to produce semiconductor integrated circuits, such as large scale semiconductor integrated circuits (hereinafter referred as xe2x80x9cLSIxe2x80x9d), with greater integration and improved performance characteristics, new techniques for fabrication have been developed. One of these techniques is chemical-mechanical polishing (hereinafter referred as xe2x80x9cCMPxe2x80x9d), which is a technique frequently used in processes such as LSI manufacturingxe2x80x94in particular, CMP is used in the flattening of an inter-layer insulating film, the formation of metal plug, and the formation of buried interconnect layer in the process to form a multi-level interconnection. This technique is disclosed, for example, in U.S. Pat. No. 4,944,836.
Further, attempts have been made in recent years to utilize copper (Cu) alloy with low resistance as the material for interconnection, rather than the aluminum (Al) alloy used in the past, with the purpose of producing high-performance LSIs. However, for Cu alloy, it is difficult to carry out fine fabrication based on dry etching methods, which methods have been frequently used for the formation of Al alloy interconnects. For this reason, the xe2x80x9cdamascenexe2x80x9d method has been primarily adopted, wherein a Cu alloy thin film is deposited on an insulating film formed with grooves fabricated thereon, and the Cu alloy thin film other than that buried in the grooves is removed by CMP, and buried interconnect is thereby prepared. This technique is disclosed, for example, in JP-A-2-278822. It is generally practiced to place a barrier metal film, such as a titanium nitride (TiN) film, a tantalum (Ta) film or a tantalum nitride (TaN) film, of several tens of nm in thickness, for the purposes of improving adhesive properties and of providing Cu diffusion barrier between the Cu alloy thin film and the insulating film.
In the past, the polishing solutions used in CMP, for metal films such as the Cu alloy commonly used for interconnects, generally contained abrasive power and oxidizer (oxidizing chemicals) as the main components. The basic CMP mechanism is oxidization of the surface of a metal film by the oxidizing action of the oxidizer, and the mechanical removal of the oxides by the abrasive powder. This technique is disclosed, for example, in xe2x80x9cThe Science of CMPxe2x80x9d (edited by Masahiro Kashiwagi; published by Science Forum Co., Ltd.; Aug. 20, 1997, p.299)
Abrasive powders, such as alumina abrasive powder or silica abrasive powder, of several tens to several hundreds of nm in grain diameter, are known in the art. Most types of abrasive powder for metal CMP that are commercially available are alumina type powders.
As the oxidizer, hydrogen peroxide (H2O2), ferric nitrate (Fe(NO3)3), and potassium periodate (KIO3) are generally used. These are described, for example, in xe2x80x9cThe Science of CMPxe2x80x9d (pp.299-300). Among these substances, hydrogen peroxide has been more frequently used in recent years, due to the fact that it does not contain metal ions.
However, when interconnects and/or plugs are fabricated using the polishing solution, which contains an abrasive powder for conventional type metal CMP as the main component, the following problems occur:
(1) Development of dishing (depression on interconnect) and erosion (corrosion and scraping of the insulating film on the peripheral portion of the interconnect);
(2) Development of scratches (polishing scratches);
(3) Delamination;
(4) The need to remove abrasive powder by ishing after CMP;
(5) High cost for abrasives;
(6) High cost for abrasive supply system and iste liquid processing system; and
(7) Dust in clean room originated from CMP system.
The above problems are caused by the fact that CMP is performed using abrasive powder. In the conventional CMP methods, however, the abrasive powder is needed to quickly remove oxide layers formed by the oxidizer. If abrasive powder is not added, it is not possible to reach a polishing rate (i.e. a polishing speed) that is suitable for practical use.
In contrast, JP-A-11-135466 discloses a method for polishing metal film using a polishing solution not containing abrasive powder, and for fabricating a buried interconnect structure. According to this method, using a polishing solution containing an oxidizer, a substance to turn the oxides to water-soluble, water and, if necessary, an anti-corrosive substance (for forming inhibition layer), the surface of the metal film is mechanically scrubbed, and a buried metal interconnect can be prepared on the surface. For example, a Cu interconnect is produced using an abrasive-free polishing solution, which contains hydrogen peroxide, citric acid, and benzotriazole (hereinafter referred as xe2x80x9cBTAxe2x80x9d).
The problems (1) to (7) described hereinabove may be solved when the above abrasive-free polishing solution method is used, while a acceptable polishing rate (speed) under normal polishing conditions of 80-150 nm/min is maintained. Even when high polishing load of 300 g/cm2 or more is applied, the polishing rate reaches the saturation level and does not go beyond 200 nm/min, and thus it is not possible to increase the throughput beyond this limit. In the case wherein a commercial alumina polishing solution is used, a polishing rate as high as 300-500 nm/min may be reached by applying a high polishing load. In this case, however, the problems of scratches and delamination become more serious.
On the other hand, a number of different approaches to these difficulties are available. One such approach is presented in JP-A-7-94455, which discloses a phosphoric acid aqueous solution as one of abrasive polishing solutions for Cu (see Example 4 of the above publication). It is described therein that the ratio of polishing rate of Cu to the insulating film can be increased up to 14.5 by using the abrasive polishing solution containing phosphoric acid of 3% concentration (see FIG. 5 of the above publication, wherein the Cu content is 100%). However, using experimentation, it is very difficult to attain a polishing rate of 50 nm/min. or more under practical polishing condition (i.e. polishing load of 500 g/cm2 or less; rotational speed of platen at 90 rpm or less) by the simple combination of abrasive powder and phosphoric acid aqueous solution. If the abrasive powder is removed, the polishing rate is less than 20 nm/min. Therefore, although the ratio of polishing rate is high using this abrasive polishing solution, it is not possible to carry out polishing with a sufficient throughput and high accuracy (without developing erosion).
In the abrasive polishing solution for tungsten CMP disclosed in JP-A-10-265776, phosphoric acid or organic acid is used as a stabilizer. In this case, the stabilizer is a chemical to suppress and control the reaction between a catalyst (ferric nitrate) added in the polishing solution, and the oxidizer (hydrogen peroxide). According to experimentation, an etching rate for Cu of this polishing solution is more than 100 nm/min, and, using this solution, it is possible to polish Cu film, but a Cu interconnect is eliminated by the etching. This polishing solution is specifically directed to tungsten CMP and is not generally applicable for Cu-CMP. Thus, using the teachings of JP-A-10-265776, it is not possible to achieve high-speed polishing of Cu by simultaneously adding phosphoric acid and organic acid (in particular, lactic acid) to the polishing solution not containing abrasive powder.
A polishing solution for Cu-CMP is disclosed in JP-A-11-21546. This polishing solution includes abrasive powder, an oxidizer (e.g. ureaxe2x80x94hydrogen peroxide), a chemical to form complex salt (e.g. ammonium oxalate or organic acid such as lactic acid), a film forming agent (e.g. BTA, imidazole), and a surface active agent. It is described in the above patent publication that inorganic acid, such as phosphoric acid, may be added in order to adjust the pH value of the polishing solution, or to promote the polishing rate of the barrier metal film. The surface active agent as described in this publication is used to reduce or suppress setting, agglutination and decomposition of the abrasive powder. By experimentation, it is practically difficult to polish Cu film using the polishing solution when the abrasive powder is removed from the polishing solution described in the above publication. That is, in this polishing solution, it is essential to mechanically remove Cu oxides via the abrasive powder. Thus, using the teachings of this publication, it is not possible to achieve high-speed polishing of Cu by simultaneously adding phosphoric acid and organic acid (in particular, lactic acid) using the polishing solution not containing abrasive powder as a main component.
A polishing solution not containing abrasive powder is disclosed in JP-A-52-21222 as a chemical polishing solution to be used for Cu ornaments on camera components. The polishing solution comprises a surface active agent, hydrogen peroxide, sulfuric acid, and phosphoric acid, and this teaching provides improved luster by polishing a Cu surface using emery abrasive paper with abrasive powder attached on it. The surface active agent has an effect to provide better luster by improving wettability of the polishing surface. According to experimentation, the etching rate of the polishing solution is 1000 nm/min. or more, and it is not possible to use this as the polishing solution for fabricating a buried Cu interconnect on the level of several hundreds of nm.
JP-A-55-47382 and JP-A-6-57455 each disclose a polishing solution not containing abrasive powder. The former is a chemical polishing solution used for deburring of machine components made of aluminum. It comprises an acid (including phosphoric acid) and aluminum chelating agent of aromatic compound. A surface active agent and hydrogen peroxide are added when necessary. The latter is a chemical polishing solution for pretreatment in the plating of brass, and it includes hydrogen peroxide, oxy-quinoline, a chemical to form complex salt, and a surface active agent. Phosphoric acid and sulfuric acid are added when necessary, and it is used for adjusting luster or satin finish. The surface active agent is added for the purposes of improving the wettability and of preventing mist caused by bubbling. In any of these chemical polishing solutions, the etching rate is 100 nm/min. or more, and these are the polishing solutions for polishing (without scrubbing) based on etching action. Therefore, these are not suitable for the use as the polishing solutions to fabricate the buried Cu interconnect of the present invention. As the polishing solution used for the buried interconnect of LSI, it is necessary to provide surface flatness on the level of nanometer. The required level of flatness (i.e. luster) should be higher than the luster level achievable by these polishing solutions.
A preferred etching rate for Cu of a polishing solution is less than 10 nm/min. The reasons are as follows: The thickness of the interconnect layer of a semiconductor device, to which the polishing solution is applied, is generally 300-1000 nm. Where the polishing is performed for several minutes, and where a polishing solution with an etching rate of about 100 nm is applied, for example, the Cu on the interconnect layer may be etched as deep as several hundreds of nm. That is, dishing may reach several hundreds of nm in depth. In order to suppress the dishing to several tens of nm, the etching rate of the polishing solution is preferably limited to less than 10 nm. Further, if over-polishing time is taken into account, it is preferably less than 1 nm/min.
The addition of anti-corrosive agent to the polishing solution has been already disclosed with the purpose of suppressing the etching. A method to add an anti-corrosive agent such as BTA, imidazole, or benzimidazole to the polishing solution for Cu is disclosed in patent publications such as JP-A-11-21546, JP-A-8-83780, and JP-A-10-116804. However, in all of these cases, the method described is the addition of anti-corrosive agent to the polishing solution containing abrasive powder. It has been asserted that a sufficient polishing rate cannot be obtained if an anti-corrosive agent is added to a polishing solution not containing abrasive powder. JP-A-11-135466 disclosed that Cu could be polished if BTA is added to an abrasive-free polishing solution. However, it has been asserted that it is not practical to add an anti-corrosive agent having higher anti-corrosive property than BTA to a polishing solution, because the polishing rate, as well as the etching rate, would be reduced or suppressed.
Therefore, the need exists for a polishing method and a method for producing semiconductor devices, by which it is possible to solve the problems (1) to (7) hereinabove in the process to fabricate a buried metal interconnect, and to achieve high-speed polishing rate (700 nm/min. or more) with improved etch rate control.
To overcome the difficulties mentioned hereinabove, it is an object of the present invention to provide a polishing method, and a method for producing semiconductor devices, by which it is possible to solve problems (1) to (7) hereinabove in the process to fabricate a buried metal interconnect, and to achieve high-speed polishing rate (700 nm/min. or more) with improved etch rate control.
The above object is attained by the method for polishing a metal film, comprising the steps of using a polishing solution which contains an oxidizer, phosphoric acid, organic acid, a chemical to form inhibition layer, and water, and of mechanically scrubbing surface of the metal film.
Phosphoric acid has an effect to efficiently turn oxides (on the surface of the metal film oxidized by an oxidizer) into water-soluble state. A representative example of the phosphoric acid used is orthophosphoric acid. Unless otherwise specified, orthophosphoric acid is referred hereinafter as phosphoric acid. In addition to orthophosphoric acid, the following substances may be used: phosphorous acid (phosphonic acid), hypophosphorous acid (phosphinic acid), metaphosphoric acid, polyphosphoric acid (e.g. diphosphoric acid (pyrophosphoric acid)), or substances containing the phosphoric acid group. Among these substances, orthophosphoric acid and phosphorous acid have the highest effect to increase the polishing rate. Also, orthophosphoric acid is advantageous in that it is chemically stable and low in cost. Phosphorous acid and hypophosphorous acid are advantageous in that each is less harmful in the polishing solution as compared to orthophosphoric acid. Orthophosphoric acid and phosphorous acid are advantageous in that each is less stimulant and irritant as compared to hypophosphorous acid or metaphosphoric acid. Phosphorous acid is advantageous in that surface roughness is caused on the polishing surface less frequently as compared to orthophosphoric acid.
Organic acid has an effect to act on the surface of the metal film, together with phosphoric acid, and to efficiently turn the metal oxides to water-soluble. Compared with the case wherein the phosphoric acid or the organic acid as mentioned hereinabove is added alone, polishing performance can be improved further if the two are used together. Among the organic acids, carboxylic acid, or hydrocarboxylic acid containing hydroxyl group or carboxyl group, have the effect of increasing the polishing rate. For example, the following substances may be used: organic acid, such as citric acid, malic acid, malonic acid, succinic acid, tartaric acid, phthalic acid, maleic acid, fumaric acid lactic acid (xcex1-hydroxypropionic acid or xcex2-hydroxypropionic acid), pimelic acid, adipic acid, glutaric acid, oxalic acid, salicylic acid, glycolic acid, tricarballylic acid, benzoic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, acrylic acid, and salts of these acids. The salt has an effect to increase solubility. These chemicals may be used in combinations of two or more.
Among these acids, it is preferable to use the following substances as the organic acid added to the polishing solution of the present invention to achieve high polishing rate and low etching rate: malonic acid, tartaric acid, malic acid, citric acid, succinic acid, maleic acid, fumaric acid, glycolic acid, tricarballylic acid, lactic acid (xcex1-hydroxypropionic acid or xcex2-hydroxypropionic acid).
Among the above acids, lactic acid (xcex1-hydroxypropionic acid) is commonly used as a food additive. It has low toxicity, is less harmful as a waste liquid, has no offensive odor, has high solubility in water, and can be produced at low cost. Additionally, lactic acid has a large effect to increase the polishing rate, and serves as a solvent for the anti-corrosive agent discussed hereinbelow. Thus, it is the most desirable substance to be used as the organic acid in the polishing solution of the present invention.
As a substance to suppress excessive oxidation or etching of the metal film, it is effective to use a chemical to form an inhibition layer. On order to form the inhibition layer, a chemical is used that has an effect to decrease the etching rate of the metal to be polished when it is added to the polishing solution, thus making it possible to suppress the development of dishing on Cu interconnect, which may occur after the interconnect fabrication. Before the chemical to form inhibition layer is added to the polishing solution of the present invention, the etching rate is more than 50 nm/min. That is, it is a polishing solution having essentially a high corrosive property. By adding the chemical to form the inhibition layer to the polishing solution, an anti-corrosive effect can be provided, and thus the present invention is thereby made suitable for the use as the polishing solution for CMP. More concretely, it is preferable to obtain an etching rate of less than 10 nm/min.
As the chemical to form the inhibition layer, an anti-corrosive agent to Cu alloy is the most preferable. The following substances may be used: BTA, imidazole, benzimidazole, naphthotriazole, benzothiazole, or a derivative of these substances. Imidazole is suitable because it has high solubility in water. Imidazole derivative is suitable because its solubility can be increased by lactic acid and it can increase the polishing rate for Cu. BTA derivative is suitable because it can suppress the etching rate for Cu.
As the BTA derivative, the following substances may be used: 4-methyl-1.H-benzotriazole, tolyltriazole, 4-carboxyl-1.H-benzotriazole, 5-methyl-1.H-benzotriazole, tolyltriazole, benzotriazole butyl ester, 5-chloro-1.H-benzotriazole, 1-chlorobenzotriazole, 1-hydroxybenzo-triazole, 1-dihydroxybenzotriazole, 2,3-dicarboxylpropyl benzotriazole, 4-hydroxybenzotriazole, 4-carboxyl-1.H-benzotriazole methyl ester, 4-carboxyl-1.H-benzotriazole butyl ester, 4-carboxyl-1.H-benzotriazole octyl ester, 5-hexyl benzotriazole, [1,2,3-benzotriazolyl-1-methyl][1,2,4-triazolyl-1-methyl][2-ethylhexyl]amine, 5,6-dimethyl-1.H-benzotriazole, etc.
As the imidazole derivative, the following substances may be used: 4-methylimidazole, 4-methyl-5-hydroxymethyl-imidazole, 1-phenyl-4-methylimidazole, 1-(p-tolyl)-4-methylimidazole, long-chain alkyl imidazole, etc.
As the benzimidazole derivative, the following substances may be used: 2-mercapto benzimidazole, 2-(n-methylpropyl)-benzimidazole (n=1, 2), 2-(n-methylbutyl-benzimidazole (n=1, 2, 3), 2-(1-ethylpropyl)-benzimidazole, 2-(1-ethylpropyl)-methylbenzimidazole, 2-n-alkyl-methylbenzimidazole, 2-(4-butylphenyl)-benzimidazole, 2-phenylmethyl-methylbenzimidazole, 2-cycloalkyl-benzimidazole, etc.
As the benzthiazole derivative, 2-mercapto benzthiazole, 2,1,3-benzthiazole, etc. may be used.
As the other anti-corrosive agent, the following substances may be used: benzofuroxan, o-phenylenediamine, M-phenylenediamine, catechol, o-aminophenol, 2-mercapto benzooxazole, melamine, thiourea, etc.
It is very effective to add a solvent for increasing solubility of the chemical to form the inhibition layer in the polishing solution. In a case wherein the temperature of the polishing solution is decreased to nearly 0 degrees Celsius, or in the case wherein the other additive is added, the solubility of the chemical to form the inhibition layer is decreased to lower than the solubility in pure water, and thus it may be crystallized and deposited in the polishing solution. Thus, it is preferable that it is set to a solubility more than twice as high as the solubility in pure water at room temperature. For example, in a case wherein BTA is used as the chemical to form the inhibition layer, the solubility of BTA is increased by more than two times by adding methanol of about 1% to the polishing solution. The same effect can be obtained by adding ethanol or isopropyl alcohol, ethylene glycol, polyethylene glycol, methyl ethyl ketone, or heptanol. Also, hydroxy acid such as lactic acid, citric acid, etc. has an effect to increase the solubility. In particular, it is more preferable to use lactic acid than citric acid because lactic acid can provide a greater increase the polishing rate. However, in some cases, citric acid is more preferable in view of the increase of solubility.
As the other chemical to form inhibition layer, a surface active agent or a thickener may be used. These polymers are adsorbed on interface between the polishing solution and the metal during CMP, and form a polymer inhibition film. This has an effect to suppress the etching. Because these substances are not selectively adsorbed on Cu, it is suitable for general-purpose application.
Among these polymers, it is more preferable to use the polymer containing carboxyl group for the purpose of improving the polishing rate on the metal. For example, polyacrylic acid, polymethacrylic acid and ammonium salt of these acids, triethanolamine salt, monoethanolamine salt, triethylamine salt, diisopropanolamine salt, etc. may be used.
A polymer having higher molecular weight provides a greater effect to form inhibition layer. In particular, a ladder polymer having a high thickening effect has an effect to increase the polishing rate. For example, crosslinking type polyacrylic acid, and its salt, are suitable for this purpose.
Among the surface active agents are polymers having anti-bacterial or anti-fungal effect. These polymers have the effect to increase the polishing performance, and are useful to prevent the growth of fungi or bacteria in the polishing solution during storage, or in iste liquid. For example, cetyl pyridinium chloride may be used for this purpose.
When two types of the chemicals to form the inhibition layer are mixed and used, it is possible to increase the polishing rate more than the case wherein these are separately used. For example, anti-corrosive agent and surface active agent, or anti-corrosive agent and thickener may be used in combination. More concretely, a substance is selected from a first group, which comprises BTA, imidazole and a derivative of these substances, and a substance is selected from a second group, which comprises polyacrylic acid, crosslinking type polyacrylic acid or ammonium salt and cetyl pyridinium chloride. Then, these two types of substances are used in combination.
The oxidizer is a substance having an effect to oxidize the surface of the metal film to be polished. Hydrogen peroxide is the most suitable, because it contains no metallic component. Also, nitric acid, ferric nitrate, or potassium periodate may be used, because these have sufficient oxidizing potency if the metal components give no hindrance. These oxidizers may be used in combination of two types or more.
Regarding the abrasive powder, in a case wherein alumina abrasive powder or silica abrasive powder is contained in the polishing solution of the present invention, an effect to increase the polishing rate is further obtained. However, the problems as described hereinabove ((1) to (7)) may occur, and the abrasive powder can be used when there is no such problem. The content of the abrasive powder in the polishing solution varies according to each individual purpose, as discussed hereinbelow. The purpose to suppress the development of dishing and erosion can be attained by setting the concentration of the abrasive powder to less than 0.05 weight %. For the purpose of decreasing the scratches on the surface of the insulating film, the concentration of the abrasive powder should be decreased to less than 0.5 weight %. For the purpose of reducing the scratches on the surface of the metal film, the concentration of the abrasive powder should be set to less than 0.1 weight %. For the purpose of decreasing delamination, the concentration of the abrasive powder should be set to less than 0.3 weight %. For the purpose of improving ishability, the concentration of the abrasive powder should be set to less than 0.01 weight %. For the purpose of decreasing the cost of the polishing solution, the concentration of the abrasive powder should be set to less than 0.001 weight %. For the purpose of solving the problem of the cost for the abrasive supply system or iste liquid processing system, the concentration of the abrasive should be set to less than 0.0001 weight %. For the purpose of suppressing and reducing the dust in the clean room, the abrasive powder should not be added.
In the fabrication of the buried Cu interconnect, if an abrasive-free polishing solution is used for the polishing of the Cu, and the polishing solution containing abrasive powder is used for the polishing of the barrier metal, i.e. if two-step polishing is performed, the problems (1), (2), (5) and (6) described hereinabove can be extensively improved. A single CMP system provided with two or more polishing platens may be used, or two CMP systems provided with a polishing platen may be used. In this case, using the abrasive-free polishing solution, the polishing can be performed at higher rate compared with the polishing of the barrier metal film, and difficulties such as polishing residues of Cu film and barrier metal film in lower depression can be avoided. As to the methods to supply the polishing solution, one method separately supplies the solution to the polishing platen for Cu and the polishing platen for the barrier metal. On the other hand, there is also a method to supply the abrasive-free polishing solution to the polishing platen for Cu and to the polishing platen for barrier metal, and further, the solution containing abrasive powder is supplied to the polishing platen for barrier metal.
Also, it is possible to use a polishing pad (stationary abrasive pad) with abrasive powder buried in it, or to use a grindstone. As a result, the content of the abrasive powder in the polishing solution can be decreased, and this makes it easier to solve the problem of iste liquid processing in (6) as described hereinabove. In the case wherein a stationary abrasive pad or grindstone is used instead of free abrasive, it is advantageous because surface flatness can be improved even when CMP is performed in one step, thus solving the problem (1) as described hereinabove.
In the case wherein polishing is performed in two steps as described hereinabove, a polishing selection ratio can be changed between the first step and the second step. One effective method is to decrease the polishing rate for Cu in the second step in order to suppress the development of erosion and dishing. For this purpose, it is recommended to increase the concentration of the chemical to form inhibition layer in the polishing solution in the second step, and to increase the polishing rate for barrier metal film as compared with the polishing rate for Cu. For example, by increasing the concentration of the anti-corrosive agent, it is possible to increase the selection ratio for the barrier metal/Cu by more than two times. Even when it is not added to the polishing solution, if BTA aqueous solution of high concentration (about 1%) is supplied to the polishing platen at the same time as the polishing solution, the same effect can be provided.
When CMP is performed in two steps, a chemical exclusively used for the barrier may be used. For example, an abrasive-free polishing solution comprising hydrogen peroxide and aromatic nitro compound may be used for TiN. The aromatic nitro compound has an effect as an oxidizer to promote the etching of titanium compound. When necessary, the above chemical to form the inhibition layer may be added. Compared with the polishing solution containing abrasive powder, the polishing rate is low, but the process for fabricating the Cu interconnect can be turned to a completely abrasive-free process.
As the aromatic nitro compound as described above, the following substances may be used: nitrobenzene sulfonic acid, nitrophenol sulfonic acid, 1-nitronaphthalene-2-sulfonic acid, sulfonic acid salt of these compounds, nitro-benzoic acid, 4-chlor-3-nitro-benzoic acid, nitro-phthalic acid, isonitro-phthalic acid, nitro-terephthalic acid, 3-nitro-salicylic acid, 3,5-dinitrosalicylic acid, picric acid, aminonitro-benzoic acid, nitro-1-naphthoic acid, or carboxylic acid salt of these compounds may be used. The salts as described hereinabove include sodium salt, potassium salt, ammonium salt, etc. As the chemical to be used for the semiconductor devices, it is most preferable to use ammonium salt. Next, it is preferable to use potassium salt because it has lower diffusion coefficient in semiconductor devices. These chemicals may be used alone or in combinations of two or more. Among these aromatic nitro compounds, nitrobenzene sulfonic acid and its salt are most preferable because the polishing rate and the etching rate for TiN are high. The aromatic nitro compound may be used in the polishing solution and the etching solution of the present invention at a concentration of 0.1-30 weight %, or more preferably 1-20 weight %.
Instead of the two-step polishing as described hereinabove, there is a complete abrasive-free process combined with drying etching method. Specifically, the abrasive-free CMP is performed for Cu in the first step, and barrier metal film is removed by dry etching method in the second step, and a damascene Cu interconnect can be fabricated. This makes it possible to solve the problems of (1) to (7) as described hereinabove. As the gas to be used in the dry etching method for barrier metal, sulfur hexafluoride (SF6) is the most suitable. SF6 generates a large amount of F radicals due to plasma dissociation, and it is advantageous to use this for selectively removing TiN or TaN. Further, the reactivity with Cu appears to be low. It is preferable that an etching selection ratio of Cu to barrier metal is 3 or more. To extend the process margin further, it is preferably 5 or more.
The polishing of the present invention can be applied for the metal film to be polished such as Cu, Ti, TiN, Ta, TaN, WN, WSiN, etc. In particular, Cu has high polishing rate when the abrasive-free polishing solution is used, and it is the most suitable as the metal to be polished by the method of the present invention. In case of Ti, TiN, Ta, TaN, WN, or WSiN, the polishing rate when the abrasive-free polishing solution is used is not as high as that of Cu, but the method can be applied by using the polishing solution containing abrasive powder.
When CMP is performed using the polishing solution of the present invention, which comprises oxidizer, phosphoric acid, organic acid and the chemical to form the inhibition layer, the surface of Cu film is first covered with and protected by the chemical to form the inhibition layer. A projected portion 27 on the surface of Cu film as shown in FIG. 2(a), and is constantly subjected to mechanical scrubbing of the abrasive cloth. The inhibition or protective layer formed by the chemical to form the inhibition layer is easily removed. The surface of Cu film exposed to the polishing solution is oxidized by the oxidizer, and a thin oxide layer is formed on the surface. Next, when phosphoric acid and organic acid are supplied, the oxide layer is turned to aqueous solution and is eluted. As a result, the thickness of the oxide layer is reduced. The portion with thinner oxide layer is exposed again to the oxidizer, and the thickness of the oxide layer is increased. These reactions are repeated, and CMP process is continued. Therefore, on the projected portion 27 on the surface of Cu film, reaction products on the surface can be easily removed. Because of local heating, reaction is accelerated, and the repeated reactions of oxidation and actions to turn to a water-soluble state proceed more rapidly than on the recess 26, where the anti-corrosive protective film is formed. That is, the polishing rate is increased on the projected portion 27 and it is thereby flattened.
The chemical to form inhibition layer is attached on the surface of the metal film, and suppresses the reaction on the recess 26, and further prevents the development of dishing. The chemical to form inhibition layer commonly used as an anti-corrosive agent, such as BTA derivative, forms a very firm protective film on the surface of Cu film. Also, a polymer having a surface active effect, such as polyacrylic acid, forms a polymer film on the interface between the polishing solution and the Cu surface, and provides an effect as the anti-corrosive agent.
Regarding the concentration of the chemical to form the inhibition layer in the polishing solution, it is preferable that the polishing rate should be maintained at 700 nm/min. or more, and etching rate should be 10 nm/min. or less (Speed ratio: 70 or more). More preferably, it is 1 nm/min. or less (speed ratio: 700 or more). If the chemical to form the inhibition layer is added at a concentration higher than this, CPM rate may be decreased. If it is added at a concentration lower than this, the etching rate is increased. As a result of the lower concentration, CMP can be carried out, but dishing would develop more frequently.